Nylon 66 / polyphenyl ether alloy as well as preparation method and application thereof

Abstract

The invention relates to a nylon 66 / polyphenyl ether alloy as well as a preparation method and application thereof. The nylon 66 / polyphenyl ether alloy comprises the following components in parts by weight: 85-95 parts of nylon 66, 2-13 parts of polyphenyl ether and 2-5 parts of a compatilizer, the compatilizer comprises bisphenol A type epoxy resin diglycidyl ether. The nylon 66 / polyphenyl ether alloy which is high in performance, low in cost and capable of remarkably improving the hydrolysis aging resistance of the material on the premise that the original performance of the nylon 66 is not remarkably influenced is obtained by mixing polyphenyl ether with a specific proportion into the nylon 66 and selecting a proper compatilizer.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a nylon 66 / polyphenylene ether alloy, its preparation method, and its application. Background Technology

[0002] Nylon 66 (PA66) is a high-performance engineering plastic widely used in automotive, electronics, and machinery industries due to its high strength, high rigidity, good wear resistance, and heat resistance. However, the amide bonds (-NH-CO-) in the Nylon 66 molecular structure are prone to hydrolysis under high temperature and humidity conditions, leading to molecular chain breakage and a sharp decline in mechanical properties (such as tensile strength and impact strength), severely limiting its long-term application in harsh environments (such as engine compartments and cooling system components). Polyphenylene oxide (PPO) is a non-crystalline engineering plastic known for its extremely low water absorption, excellent dimensional stability, and hydrolysis resistance. However, PPO has extremely poor compatibility with Nylon 66; simple blending leads to phase separation and weak interfacial bonding, thus deteriorating the mechanical properties of the blend. Therefore, the industry typically does not use PPO in small amounts as a hydrolysis-resistant modifier for Nylon 66.

[0003] Most existing Nylon 66 / polyphenylene ether alloy solutions use polyphenylene ether as a reinforcing agent in combination with nylon materials, and maleic anhydride grafts as compatibilizers to improve the interfacial bonding between polyphenylene ether and nylon 66 (e.g., CN109867952A). However, the large-scale addition of polyphenylene ether as a reinforcing agent and the use of maleic anhydride grafts as compatibilizers make it difficult to improve the long-term hydrolysis resistance of nylon 66 without significantly affecting its original properties. Furthermore, the preparation process of maleic anhydride grafts is relatively complicated and costly, limiting their widespread use in cost-sensitive applications.

[0004] Therefore, how to provide a high-performance, low-cost nylon 66 / polyphenylene ether alloy that significantly improves the hydrolytic aging resistance without significantly affecting the original properties of nylon 66 has become an urgent problem to be solved. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides a nylon 66 / polyphenylene ether alloy, its preparation method, and its application. By mixing a specific proportion of polyphenylene ether into nylon 66 and selecting a suitable compatibilizer, a high-performance, low-cost nylon 66 / polyphenylene ether alloy is obtained, which can significantly improve the material's resistance to hydrolytic aging without significantly affecting the original properties of nylon 66.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides a nylon 66 / polyphenylene ether alloy, wherein the nylon 66 / polyphenylene ether alloy comprises the following components by weight: 85-95 parts of nylon 66, 2-13 parts of polyphenylene ether, and 2-5 parts of compatibilizer;

[0008] The compatibilizer includes bisphenol A type epoxy resin diglycidyl ether.

[0009] Among them, 85-95 portions can be, for example, 85 portions, 86 portions, 88 portions, 90 portions, 92 portions, 94 portions, or 95 portions; 2-13 portions can be, for example, 2 portions, 3 portions, 4 portions, 5 portions, 6 portions, 8 portions, 10 portions, 12 portions, or 13 portions; 2-5 portions can be, for example, 2 portions, 3 portions, 4 portions, or 5 portions.

[0010] This invention improves the hydrolytic aging resistance of nylon 66 by incorporating polyphenylene ether into it. Furthermore, the invention employs a bisphenol A type epoxy resin diglycidyl ether compatibilizer, which effectively reduces the interfacial energy between the nylon 66 and polyphenylene ether phases, improving material compatibility, forming a stable microstructure, and hindering water molecule penetration. This further enhances the hydrolytic aging resistance of the alloy material without significantly affecting the original properties of nylon 66.

[0011] Preferably, the melting point of the nylon 66 is 260-265℃, for example, it can be 260℃, 261℃, 262℃, 263℃, 264℃ or 265℃, etc.

[0012] Preferably, the number average molecular weight of the nylon 66 is 15,000-30,000, for example, it can be 15,000, 16,000, 18,000, 20,000, 22,000, 24,000, 25,000, 26,000, 28,000 or 30,000.

[0013] Preferably, the number average molecular weight of the polyphenylene ether is 10,000-25,000, for example, it can be 10,000, 12,000, 14,000, 15,000, 16,000, 18,000, 20,000, 22,000, 24,000 or 25,000.

[0014] Preferably, the nylon 66 / polyphenylene oxide alloy further comprises, by weight, any one or a combination of at least two of the following: 0.2-0.5 parts antioxidant, 0.5-1 parts lubricant, or 0.2-0.5 parts colorant.

[0015] Among them, 0.2-0.5 parts can be, for example, 0.2 parts, 0.3 parts, 0.4 parts, or 0.5 parts; 0.5-1 part can be, for example, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, or 1 part.

[0016] Preferably, the antioxidant comprises any one or a combination of at least two of the following: pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,6-tributyl-4-methylphenol, bis(3,5-tributyl-4-hydroxyphenyl) sulfide, triethylene glycol bis-β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, or N,N'-bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine.

[0017] Preferably, the lubricant comprises any one or a combination of at least two of calcium stearate, pentaerythritol stearate, ethylene wax, or silicone oil.

[0018] Preferably, the pigment includes carbon black and / or titanium dioxide.

[0019] In a second aspect, the present invention provides a method for preparing the nylon 66 / polyphenylene ether alloy as described in the first aspect, the method comprising the following steps:

[0020] The components of the nylon 66 / polyphenylene ether alloy are mixed and then melt co-extruded to obtain the nylon 66 / polyphenylene ether alloy.

[0021] Preferably, the mixing is carried out under stirring.

[0022] Preferably, the stirring speed is 550-650 rpm, for example, 550 rpm, 560 rpm, 580 rpm, 600 rpm, 620 rpm, 640 rpm or 650 rpm.

[0023] Preferably, the mixing time is 10-20 min, for example, it can be 10 min, 12 min, 14 min, 15 min, 16 min, 18 min or 20 min.

[0024] Preferably, the melt co-extrusion is carried out in a twin-screw extruder.

[0025] Preferably, the rotational speed of the twin-screw extruder is 450-550 r / min, for example, it can be 450 r / min, 460 r / min, 480 r / min, 500 r / min, 520 r / min, 540 r / min or 550 r / min, etc.

[0026] Preferably, the residence time of the twin-screw extruder is 2-4 min, for example, it can be 2 min, 2.5 min, 3 min, 3.5 min or 4 min, etc.

[0027] Preferably, the temperatures of the twin-screw extruder include: zone 1 temperature of 135-145℃, zone 2 temperature of 255-265℃, zone 3 temperature of 255-265℃, zone 4 temperature of 265-275℃, zone 5 temperature of 270-280℃, zone 6 temperature of 265-275℃, zone 7 temperature of 265-275℃, zone 8 temperature of 265-275℃, zone 9 temperature of 265-275℃, and zone 10 temperature of 270-280℃.

[0028] Among them, 135-145℃ can be, for example, 135℃, 136℃, 138℃, 140℃, 142℃, 144℃ or 145℃, etc.; 255-265℃ can be, for example, 255℃, 256℃, 258℃, 260℃, 262℃, 264℃ or 265℃, etc.; 265-275℃ can be, for example, 265℃, 266℃, 268℃, 270℃, 272℃, 274℃ or 275℃, etc.; 270-280℃ can be, for example, 270℃, 272℃, 274℃, 275℃, 276℃, 278℃ or 280℃, etc.

[0029] Thirdly, the present invention provides an application of the nylon 66 / polyphenylene ether alloy as described in the first aspect in automobiles, electronic and electrical equipment, and mechanical equipment.

[0030] Compared with the prior art, the present invention has at least the following beneficial effects:

[0031] (1) By mixing polyphenylene ether into nylon 66 material and compounding it with bisphenol A type epoxy resin diglycidyl ether compatibilizer, the present invention effectively reduces the interfacial energy between the two phases of nylon 66 and polyphenylene ether, improves the compatibility of the material, forms a stable micro-phase structure, hinders the penetration of water molecules, and further improves the hydrolytic aging resistance of the alloy material without significantly affecting the original properties of nylon 66.

[0032] (2) The preparation process of the Nylon 66 / polyphenylene ether alloy provided by the present invention is simple, the compatibilizer used is low in cost, the alloy has a wide range of applications, and has broad application prospects in the fields of automobiles, electronics and electrical appliances, and mechanical equipment.

[0033] (3) Compared with pure nylon 66 material, after 500 h of hydrolytic aging, its tensile strength retention rate is only 55% of the original tensile strength, and its notched impact strength retention rate is only 40% of the original notched impact strength. After 1000 h of hydrolytic aging, its tensile strength retention rate is only 34% of the original tensile strength, and its notched impact strength retention rate is only 21% of the original notched impact strength. The sample has become brittle and broken. However, the nylon 66 / polyphenylene ether alloy provided by the present invention still maintains 84-95% of the original tensile strength after 500 h of hydrolytic aging, and 63-92% of the original tensile strength after 1000 h of hydrolytic aging. The notched impact strength of the nylon 66 / polyphenylene ether alloy still maintains 47-88% of the original notched impact strength after 500 h of hydrolytic aging, and 30-71% of the original notched impact strength after 1000 h of hydrolytic aging. The performance degradation rate is much slower than that of pure nylon 66. Detailed Implementation

[0034] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.

[0035] The specific information of the materials used in the following specific embodiments of the present invention is as follows:

[0036] Nylon 66, Zytel 101L, melting point 260-265℃, purchased from DuPont, USA.

[0037] Polyphenylene oxide, LXN040, purchased from Nantong Xingchen Company;

[0038] Bisphenol A type epoxy resin diglycidyl ether (DGEBA) was purchased from KUKDO Chemical.

[0039] Antioxidant, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], antioxidant 1010;

[0040] Lubricant, calcium stearate;

[0041] Pigment, N330, purchased from Jiangxi Black Cat Carbon Black Co., Ltd.

[0042] Examples 1-8 and Comparative Examples 1-5

[0043] Examples 1-8 and Comparative Examples 1-5 respectively provide a nylon 66 / polyphenylene ether alloy and its preparation method. The specific composition of the nylon 66 / polyphenylene ether alloy is shown in Table 1 (the amount of each component in the table is by weight), where "--" indicates that the component was not added.

[0044] The preparation method of the nylon 66 / polyphenylene ether alloy includes:

[0045] The components of the nylon 66 / polyphenylene ether alloy were added to a high-speed mixer according to their weight proportions and mixed at 600 rpm for 15 min. The mixed raw material was then fed into a twin-screw extruder for melt co-extrusion. The extruder temperatures were: zone 1 140℃, zone 2 260℃, zone 3 260℃, zone 4 270℃, zone 5 275℃, zone 6 270℃, zone 7 270℃, zone 8 270℃, zone 9 270℃, and zone 10 275℃. The extruder screw speed was 500 rpm, and the residence time was 3 min. After extrusion, the material was cooled, dried, and pelletized to obtain the nylon 66 / polyphenylene ether alloy.

[0046] Table 1

[0047]

[0048] Test methods

[0049] The nylon 66 / polyphenylene ether alloys obtained in Examples 1-8 and Comparative Examples 1-5 were subjected to performance tests, and the test methods / standards are as follows:

[0050] Tensile strength (MPa): Referring to ISO527-2 standard, the tensile strength of nylon 66 / polyphenylene ether alloy was tested before hydrolysis, after 500 h of hydrolysis aging (temperature: 70℃±2℃, relative humidity: 62%RH±5%RH), and after 100 h of hydrolysis aging (temperature: 70℃±2℃, relative humidity: 62%RH±5%RH), and the tensile strength retention rate (%) before and after aging was calculated.

[0051] Notched impact strength (kJ / m) 2 Referring to ISO179 standard, the notched impact strength of nylon 66 / polyphenylene ether alloy was tested before hydrolysis, after 500 h of hydrolysis aging (temperature: 70℃±2℃, relative humidity: 62%RH±5%RH), and after 100 h of hydrolysis aging (temperature: 70℃±2℃, relative humidity: 62%RH±5%RH).

[0052] The test results are shown in Table 2-3 below:

[0053] Table 2

[0054]

[0055] Table 3

[0056]

[0057] The test results show that:

[0058] (1) As can be seen from Examples 1 to 8, although the tensile strength of the material is slightly reduced by mixing polyphenylene ether into nylon 66, the hydrolysis resistance of the material is significantly improved and the impact strength is slightly improved. This indicates that the compatibilizer used in this invention has a good toughening effect and improves the long-term hydrolysis resistance without significantly affecting the original performance of nylon 66.

[0059] (2) As can be seen from Examples 1, 4-8 and Comparative Examples 3-6, the present invention can achieve better toughening and hydrolysis resistance by further limiting the amount of polyphenylene ether and compatibilizer added. If the amount of polyphenylene ether added is too low, the aging resistance of the alloy material will decrease. If the amount of polyphenylene ether added is too high, the mechanical properties of the nylon 66 / polyphenylene ether alloy will be poor. If the amount of compatibilizer added is too low, the notch retention rate of the nylon 66 / polyphenylene ether alloy will be low. If the amount of compatibilizer added is too high, the mechanical properties of the nylon 66 / polyphenylene ether alloy will be poor.

[0060] (3) As can be seen from Example 1 and Comparative Example 1, compared with pure nylon 66 material, after 500 h of hydrolytic aging, its tensile strength retention rate is only 55% of the original tensile strength, and its notched impact strength retention rate is only 40% of the original notched impact strength. After 1000 h of hydrolytic aging, its tensile strength retention rate is only 34% of the original tensile strength, and its notched impact strength retention rate is only 21% of the original notched impact strength. The sample has become brittle and broken. However, the nylon 66 / polyphenylene ether alloy provided by the present invention still maintains 84-95% of the original tensile strength after 500 h of hydrolytic aging, and 63-92% of the original tensile strength after 1000 h of hydrolytic aging. The notched impact strength of the nylon 66 / polyphenylene ether alloy still maintains 47-88% of the original notched impact strength after 500 h of hydrolytic aging, and 30-71% of the original notched impact strength after 1000 h of hydrolytic aging. The performance degradation rate is much slower than that of pure nylon 66.

[0061] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A nylon 66 / polyphenylene oxide alloy, characterized in that, The nylon 66 / polyphenylene ether alloy comprises the following components by weight: 85-95 parts nylon 66, 2-13 parts polyphenylene ether, and 2-5 parts compatibilizer; The compatibilizer includes bisphenol A type epoxy resin diglycidyl ether.

2. The nylon 66 / polyphenylene oxide alloy according to claim 1, characterized in that, The melting point of the nylon 66 is 260-265℃.

3. The nylon 66 / polyphenylene oxide alloy according to claim 1 or 2, characterized in that, The number-average molecular weight of the nylon 66 is 15,000-30,000; Preferably, the number average molecular weight of the polyphenylene ether is 10,000-25,000.

4. The nylon 66 / polyphenylene oxide alloy according to any one of claims 1-3, characterized in that, The nylon 66 / polyphenylene oxide alloy further includes, by weight, any one or a combination of at least two of the following: 0.2-0.5 parts antioxidant, 0.5-1 parts lubricant, or 0.2-0.5 parts colorant.

5. The nylon 66 / polyphenylene oxide alloy according to claim 4, characterized in that, The antioxidant comprises any one or a combination of at least two of the following: pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,6-tributyl-4-methylphenol, bis(3,5-tributyl-4-hydroxyphenyl) sulfide, triethylene glycol bis-β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, or N,N'-bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine.

6. The nylon 66 / polyphenylene oxide alloy according to claim 4, characterized in that, The lubricant includes any one or a combination of at least two of calcium stearate, pentaerythritol stearate, vinyl wax, or silicone oil.

7. The nylon 66 / polyphenylene oxide alloy according to claim 4, characterized in that, The pigments include carbon black and / or titanium dioxide.

8. A method for preparing the nylon 66 / polyphenylene ether alloy as described in any one of claims 1-7, characterized in that, The preparation method includes the following steps: The components of the nylon 66 / polyphenylene ether alloy are mixed and then melt co-extruded to obtain the nylon 66 / polyphenylene ether alloy.

9. The method for preparing the nylon 66 / polyphenylene ether alloy according to claim 8, characterized in that, The mixing is carried out under stirring; Preferably, the stirring speed is 550-650 rpm; Preferably, the mixing time is 10-20 min; Preferably, the melt co-extrusion is carried out in a twin-screw extruder; Preferably, the rotational speed of the twin-screw extruder is 450-550 r / min; Preferably, the residence time of the twin-screw extruder is 2-4 minutes; Preferably, the temperatures of the twin-screw extruder include: zone 1 temperature of 135-145℃, zone 2 temperature of 255-265℃, zone 3 temperature of 255-265℃, zone 4 temperature of 265-275℃, zone 5 temperature of 270-280℃, zone 6 temperature of 265-275℃, zone 7 temperature of 265-275℃, zone 8 temperature of 265-275℃, zone 9 temperature of 265-275℃, and zone 10 temperature of 270-280℃.

10. The application of the nylon 66 / polyphenylene ether alloy as described in any one of claims 1-7 in automobiles, electronic and electrical equipment, and mechanical equipment.

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